US5940156A - LCD and method for producing with a larger polymerization rate in non-pixel regions than that in pixel regions - Google Patents

LCD and method for producing with a larger polymerization rate in non-pixel regions than that in pixel regions Download PDF

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US5940156A
US5940156A US08/823,866 US82386697A US5940156A US 5940156 A US5940156 A US 5940156A US 82386697 A US82386697 A US 82386697A US 5940156 A US5940156 A US 5940156A
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liquid crystal
display device
crystal display
light
produced
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Kenji Nishiguchi
Kohichi Fujimori
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Sharp Corp
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Sharp Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133377—Cells with plural compartments or having plurality of liquid crystal microcells partitioned by walls, e.g. one microcell per pixel
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a liquid crystal display device and a method for producing the same.
  • the present invention relates to a liquid crystal display device using a liquid crystal partitioned by polymer walls as a display medium and a method for producing the same.
  • a display mode used for the display media include a twisted nematic (TN) mode, a super twisted nematic (STN) mode, an electrically controlled birefringence (ECB) mode, a ferroelectric liquid crystal (FLC) mode, and a scattering mode such as a polymer dispersed type liquid crystal (PDLC) mode.
  • TN twisted nematic
  • STN super twisted nematic
  • EBC electrically controlled birefringence
  • FLC ferroelectric liquid crystal
  • PDLC polymer dispersed type liquid crystal
  • the PDLC mode has been receiving particularly attention among the above-mentioned display modes.
  • a system which electrically controls a transparent state and an opaque state, using the birefringence of a liquid crystal is known.
  • the ordinary refractive index of liquid crystal molecules in a display medium is made identical with the refractive index of a polymer which is the display medium, and the liquid crystal molecules are aligned in the direction of an electric field under the application of a voltage so as to display a transparent state.
  • the alignment of the liquid crystal molecules is disturbed under no application of a voltage so as to display a light scattering state.
  • the PDLC mode has a problem that a threshold voltage for driving a liquid crystal increases.
  • Japanese Laid-Open Patent Publication No. 5-257135 discloses a liquid crystal display device which locally contains a polymer with a network structure in a desired pattern as a display medium interposing a liquid crystal region and a region in which the alignment of liquid crystal molecules in the liquid crystal region is fixed by polymerization of a polymerizable liquid crystal between a pair of substrates.
  • a polymer with a network structure can be formed by irradiation with light having a specific wavelength to the polymerizable liquid crystal material containing a reactive group such as a diacrylate group through a photomask.
  • the above-mentioned liquid crystal display device does not have sufficient shock resistance with respect to external pressure, while being capable of locally changing a switching threshold.
  • the polymerizable liquid crystal material is generally highly reactive, and the polymerization thereof is considered to proceed with time in a region which is not irradiated with light. Therefore, the switching threshold, the alignment of liquid crystal molecules, and the like may gradually change in this liquid crystal display device.
  • Japanese Laid-Open Patent Publication No. 6-301015 discloses a liquid crystal display device 800 as shown in FIG. 8B.
  • the liquid crystal display device 800 is produced in the following manner: As shown in FIG. 8A, a mixture 813 containing a liquid crystal material, a photopolymerizable resin, and a photopolymerization initiator is injected between a pair of substrates 801a and 801b. Then, a photomask 814 having light-blocking portions 810 and light-passing portions 811 is placed on the substrate 801a in such a manner that the light-blocking portions 810 cover pixel portions. Under this condition, the mixture 813 is irradiated with UV-light 808 through the photomask 814.
  • liquid crystal regions 806 are formed in the pixel portions which are not irradiated with light, and a polymer wall 807 is formed in portions irradiated with light other than the pixel portions.
  • the liquid crystal display device 800 having a liquid crystal medium layer is produced.
  • the difference in optical path corresponding to the thickness of the substrate 801a is formed between the photomask 814 and the portions where polymer walls are formed.
  • polymer walls which are wider than the light-passing portions of the photomask 814 are formed by light scattering, unless the light which is radiated to the substrate 801a is precisely parallel.
  • an unreacted photopolymerizable resin or the resultant polymer may remain in liquid crystal in the portions of the liquid crystal display device 800 which are light-blocked by the photomask 814, depending upon the type of photopolymerizable resin to be used. This decreases the display characteristics of the liquid crystal display device.
  • Japanese Laid-Open Patent Publication No. 7-287241 discloses a liquid crystal display device 900 as shown in FIG. 9B.
  • the liquid crystal display device 900 is produced in the following manner: As shown in FIG. 9A, a transparent electrode 902a made of a material (e.g., ITO (Indidium Tin Oxide)), which is not likely to pass light with a specific wavelength, is formed on one surface of a substrate 901a, and a transparent electrode 902b made of the same material is formed on one surface of a substrate 901b. Then, the substrates 901a and 901b are placed in such a manner that the transparent electrodes 902a and 902b are opposed to each other.
  • a transparent electrode 902a made of a material e.g., ITO (Indidium Tin Oxide)
  • a mixture at least containing a liquid crystal material, a photopolymerizable resin, and a photopolymerization initiator is injected between the substrates 902a and 902b.
  • the mixture is irradiated with light 908 having a specific wavelength through the substrates 901a and 901b.
  • liquid crystal regions 906 are formed in pixel portions which are not irradiated with light, and a polymer wall 907 is formed in portions which are irradiated with light other than the pixel portions.
  • the liquid crystal display device 900 having a liquid crystal medium layer is produced. Accordingly, in the liquid crystal display device 900 described in Japanese Laid-Open Patent Publication No. 7-287241, the transparent electrodes work as a photomask which reduces or blocks light having a specific wavelength.
  • the pixel portions composed of the liquid crystal regions 906 are also irradiated with light. Therefore, the resultant polymer remains in the pixel portions and may degrade the alignment of liquid crystal molecules and/or form insufficient pixel portions. This decreases the display characteristics of the liquid crystal display device.
  • a liquid crystal display device of the present invention includes a liquid crystal region made of a liquid crystal as a display medium and a polymer wall surrounding the liquid crystal region between a pair of substrates, wherein the polymer wall is formed by selectively radiating light having different irradiation intensities to an irradiation intensity-dependent mixture containing a photopolymerizable monomer.
  • a polymerization rate of the photopolymerizable monomer contained in the irradiation intensity-dependent mixture in a non-pixel portion is 1.1 times or more that in a pixel portion.
  • an element for selectively radiating the light having different irradiation intensities includes a light-blocking layer reducing an amount of transmitted light with respect to a wavelength.
  • the element for selectively radiating the light having different irradiation intensities is a transparent electrode made of ITO.
  • the photopolymerizable monomer contained in the irradiation intensity-dependent mixture is at least-bifunctional acrylate or methacrylate monomer.
  • the irradiation intensity-dependent mixture contains at least-bifunctional acrylate or methacrylate monomer and an acrylate or methacrylate monomer having a structure similar to a liquid crystal molecule.
  • a method for producing a liquid crystal display device including a liquid crystal region made of a liquid crystal as a display medium and a polymer wall surrounding the liquid crystal region between a pair of substrates.
  • the method includes the steps of: injecting an irradiation intensity-dependent mixture containing a liquid crystal material for forming the liquid crystal region, a photopolymerizable monomer for forming the polymer wall, and a photopolymerization initiator between the attached pair of substrates to form a liquid crystal cell; selectively radiating light having different irradiation intensities to a predetermined portion of the liquid crystal cell at a high temperature; and cooling the liquid crystal cell after the light irradiation to form the polymer wall.
  • the above-mentioned method further includes the step of radiating light to the predetermined portion of the liquid crystal cell.
  • an amount of light irradiation in the step of selectively radiating light is 1000 mJ/cm 2 to 5000 mJ/cm 2 .
  • an amount of light irradiation in the step of selectively radiating light is 1000 mJ/cm 2 to 5000 mJ/cm 2 .
  • a cooling rate in the step of cooling the liquid crystal cell after the light irradiation is 1.0° C./minute or less.
  • a cooling rate in the step of cooling the liquid crystal cell after the light irradiation is 1.0° C./minute or less.
  • the invention described herein makes possible the advantages of (1) providing a liquid crystal display device having improved separation between liquid crystal regions and polymer walls, in which the liquid crystal regions are placed in pixel portions and the polymer walls are placed in portions other than the pixel portions by phase separation; (2) providing a liquid .crystal display device with a satisfactory alignment of liquid crystal molecules; (3) providing a liquid crystal display device in which the ratio of opening in pixel portions is prevented from decreasing, and which has outstanding shock resistance with respect to external pressure; (4) providing a liquid crystal display device in which polymer walls have improved heat resistance; and (5) providing a method for producing such a liquid crystal display device in a simple manner.
  • FIG. 1 is a schematic cross-sectional view showing an exemplary liquid crystal display device according to the present invention.
  • FIG. 2 is a graph showing the relationship between the time and the heat of reaction in the course of measuring the polymerization rate of a photo-polymerizable monomer.
  • FIG. 3 is a graph showing the relationship between the time and the monomer conversion in the course of measuring the polymerization rate of a photo-polymerizable monomer used in the present invention.
  • FIG. 4 is a graph showing voltage-light transmittance characteristics of liquid crystal display devices produced in Examples 13 and 14, and Comparative Example 15.
  • FIG. 5 is a photomicrograph showing pixel portions in a liquid crystal display device produced in Comparative Example 16.
  • FIG. 6 is a photomicrograph showing a state where liquid crystal droplets are incorporated in polymer walls in a liquid crystal display device produced in Comparative Example 18.
  • FIG. 7 is a graph showing the relationship between the irradiation intensity and the polymerization rate of a photopolymerizable monomer used in the present invention.
  • FIGS. 8A and 8B are schematic views illustrating a method for producing a conventional liquid crystal display device:
  • FIG. 8A is a schematic view showing the step of radiating UV-light to a mixture containing a liquid crystal material, a photopolymerizable resin, and a photopolymerization initiator between a pair of substrates provided so as to be opposed to each other through a photomask;
  • FIG. 8B is a schematic view of a liquid crystal display device produced by the irradiation with UV-light.
  • FIGS. 9A and 9B are schematic views illustrating a method for producing a conventional liquid crystal display device:
  • FIG. 9A is a schematic view showing the step of radiating light having a specific wavelength to a mixture containing a liquid crystal material, a photopolymerizable resin, and a photopolymerization initiator between a pair of substrates each having a transparent electrode in a predetermined region;
  • FIG. 9B is a schematic view of a liquid crystal display device produced by the irradiation with light.
  • the liquid crystal display device of the present invention will be described with reference to FIG. 1.
  • the liquid crystal display device of the present invention includes a display medium interposed between a pair of substrates 101a and 101b.
  • the display medium includes liquid crystal regions 103 in portions corresponding to pixels 107.
  • the liquid crystal regions 103 are surrounded by polymer walls 104.
  • the substrate 101a has a plurality of band-shaped transparent electrodes 102a made of a material such as ITO formed in parallel with each other on the display medium side.
  • the substrate 101b also has a plurality of transparent electrodes 102b made of a material such as ITO on the display medium side.
  • the transparent electrodes 102a and 102b interpose the display medium so as to cross each other.
  • an electrical insulating layer and an alignment layer are formed in this order between the transparent electrode 102a and the display medium and between the transparent electrode 102b and the display medium.
  • a preferable method for producing a liquid crystal display device according to the present invention will be exemplified.
  • a plurality of band-shaped transparent electrodes 102a and 102b are formed by sputtering in parallel with each other at a predetermined interval (e.g., about 20 ⁇ m), respectively on one surface of the substrates 101a and 101b made of a material such as glass.
  • the width of the transparent electrodes 102a and 102b to be formed is not particularly limited, but for example, about 280 ⁇ m. Pixel portions become bigger along with the increase in the width of the transparent electrodes 102a and 102b.
  • the thickness of the transparent electrodes 102a and 102b to be formed is not particularly limited, but for example, about 200 nm.
  • the transparent electrodes 102a and 102b has a light transmittance of about 36%, for example, with respect to the light having a wavelength of 365 nm.
  • Non-electrode portions 108 of the substrate 101a have a light transmittance of about 90%, for example, with respect to the light having a wavelength of 365 nm. It is known that the light transmittance of the transparent electrode decreases with the increase in the thickness of the transparent electrode.
  • an electrical insulating layer can be formed so as to cover the transparent electrodes 102a and 102b.
  • the electrical insulating layer is formed by sputtering using SiO 2 or the like.
  • the thickness of the electrical insulating layer to be formed is preferably about 50 nm to about 300 nm, and more preferably about 70 nm to about 100 nm.
  • an alignment layer made of an organic material such as polyimide can be formed on the electrical insulating layer.
  • the thickness of the alignment layer to be formed is preferably about 30 nm to about 200 nm, and more preferably about 50 nm to about 100 nm.
  • the alignment layer thus formed is subjected to rubbing with a nylon cloth or the like.
  • substrates with an alignment layer formed thereon can be used for producing liquid crystal display devices in a TN mode, an STN mode, and the like, and substrates without an alignment layer formed thereon can be used for producing liquid crystal display devices in an axis-symmetrical alignment mode, and the like.
  • the substrates 101a and 101b produced as described above are attached to each other in such a manner that the band-shaped transparent electrodes 102a and 102b cross each other with spacers 5 made of a known material interposed therebetween. Then, the ends of the substrates 101a and 101b are attached to each other with a known sealant 6.
  • the transparent electrodes 102a and 102b formed on the substrates 101a and 101b should be placed so as to cross each other. They may not cross at right angles.
  • an injection hole (not shown) is formed in a portion of the periphery of the substrates 101a and 1b.
  • an irradiation intensity-dependent mixture containing a liquid crystal material, and a photopolymerizable monomer is injected between the substrates 101a and 101b through the injection hole, whereby a liquid crystal cell is formed.
  • irradiation intensity-dependent mixture herein refers to a mixture at least containing a liquid crystal material and a photopolymerizable monomer whose polymerization rate changes depending upon the intensity of the light.
  • the liquid crystal material used in the present invention can be any liquid crystal materials used in conventional liquid crystal display devices in a TN mode, an STN mode, an ECB mode, an FLC mode, a light scattering mode, an axis-symmetrical alignment mode, and the like.
  • liquid crystal materials include ZLI-4427 containing 0.3% by weight of a chiral agent (S-811) (produced by Merck & Co., Inc.).
  • the photopolymerizable monomer used in the present invention forms the polymer walls 104 by selectively radiating light having different irradiation intensity as described later.
  • Examples of the photopolymerizable monomer used in the present invention include styrene type photopolymerizable monomers such as p-phenylstyrene; monofunctional (meth)acrylate such as adamanthyl acrylate, isobornyl acrylate, perfluoromethacrylate, R-694 (produced by Nippon Kayaku Co., LTD.), stearyl acrylate, and t-butylmethacrylate; bifunctional (meth)acrylate such as SR-2000 (produced by Nippon Kayaku Co., LTD.), R-684 (produced by Nippon Kayaku Co., LTD.), and hexanediol dimethacrylate (HDDMA); and bifunctional or more (meth)acrylate such as trimethylol propane trimethacrylate (TMPTMA); and mixtures thereof.
  • styrene type photopolymerizable monomers such as p-phenylstyrene
  • the at least-bifunctional (meth)acrylate monomers are preferable.
  • the polymer obtained from the at least-bifunctional (meth)acrylate monomers has crosslinkages.
  • the molecular structure of the polymer is different from those of the monomers before the polymerization.
  • Such a polymer cannot be dissolved in a liquid crystal.
  • liquid crystal regions and polymer walls are sufficiently separated in the liquid crystal display device to be obtained by using these monomers.
  • the crosslinkage in the polymer obtained from the monomers the polymer walls in the liquid crystal display device has improved heat resistance.
  • the photopolymerizable monomer it is further preferable to use, together with the above-mentioned bifunctional or more (meth)acrylate monomer, acrylate or methacrylate having a structure similar to a liquid crystal molecule, represented by the following formula (I): ##STR1## where A is ##STR2## B is none, or ##STR3## X is none, or ##STR4## R is H or methyl; and n is an integer of 0 to 9, preferably 3 to 5.
  • the monomer represented by formula (I) is known in the art.
  • the photopolymerizable monomer having a structure similar to a liquid crystal molecule has a high compatibility with the liquid crystal material.
  • the polymerization rate of the photopolymerizable monomer during light irradiation can be controlled by changing the contents of the liquid crystal material and the photopolymerizable monomer in the mixture.
  • the phase separation between the liquid crystal regions and the polymer walls can be sufficiently achieved.
  • the liquid crystal material and the photopolymerizable monomer are contained in the irradiation intensity-dependent mixture in such a manner that the polymerization rate of the photopolymerizable monomer in non-pixel portions becomes 1.1 times or more than that in pixel portions.
  • the phase separation between the liquid crystal regions and the polymer walls may not be sufficiently achieved in the liquid crystal display device to be obtained.
  • the irradiation intensity-dependent mixture can contain a photopolymerization initiator.
  • a photopolymerization initiator which can be contained in the mixture include Irgacure 651 (produced by CIBA-GEIGY Corporation). Type and amount of the photopolymerization initiator to be used are not particularly limited.
  • the irradiation intensity-dependent mixture containing the above-mentioned liquid crystal material, photopolymerizable monomer, and photopolymerization initiator is injected between a pair of substrates 101a and 101b attached to each other through the injection hole at a predetermined temperature (e.g., about 30° C.). Then, the injection hole can be sealed with a known UV-curable resin by using UV-light or with a known adhesive such as a two pack adhesive and an instant adhesive. In the case where the injection hole is sealed with a UV-curable resin, it is desirable to radiate UV-light only to the injection hole.
  • predetermined portions of the liquid crystal cell are irradiated with light.
  • the "predetermined portions” can vary depending upon the purpose; however, they typically refer to the pixel portions and the non-pixel portions of the substrates 101a and 101b.
  • the light is simultaneously radiated through the substrates 101a and 101b, or through one substrate and then through the other substrate. Alternatively, the light is radiated only through one substrate.
  • a plurality of liquid crystal regions 103 arranged in a row are formed so as to be placed in a stripe shape with respect to the transparent electrodes 102a formed in parallel with each other.
  • a light source for conducting such light irradiation for example, a high-pressure mercury lamp for UV-light irradiation capable of emitting parallel light can be used.
  • the amount of light irradiation is preferably 1000 mJ/cm 2 to 5000 mJ/cm 2 , and more preferably 1200 mJ/cm 2 to 4000 mJ/cm 2 . Even in the case where light having a different wavelength is radiated, the amount of light irradiation is preferably in this range.
  • the liquid crystal display device to be obtained may not have outstanding display characteristics.
  • the amount of light irradiation can be appropriately prescribed as needed without being limited to the above range.
  • a light-blocking layer made of an inorganic layer or an organic layer capable of reducing the amount of transmitted light with respect to a specific wavelength is used.
  • this electrode works as a light-blocking layer.
  • a photomask having regions having selectively different amounts of transmitted light can be used as a light-blocking layer.
  • the above-mentioned light irradiation is conducted at high temperatures.
  • the light irradiation at high temperatures allows the liquid crystal between the substrates 101a and 101b to assume an isotropic state and the polymerization reaction to be uniformly effected.
  • the liquid crystal regions 103 are formed in pixel portions corresponding to the overlapping portions of the transparent electrodes 102a and 102b between the substrates 101a and 101b, and the polymer walls 104 are formed in non-pixel portions other than the pixel portions. As a result, the liquid crystal regions 103 are surrounded by the polymer walls 104.
  • the term "surround" used in the present specification refers to a state where the liquid crystal cell is partitioned by the polymer walls 104, as well as a state where the entire periphery of each liquid crystal region 103 is surrounded by the polymer wall 104.
  • the liquid crystal cell is slowly cooled to room temperature in a cooling chamber.
  • the cooling rate used in this step is preferably 1.0° C./minute or less, and more preferably 0.05° C./minute to 1.0° C./minute.
  • the polymer walls in the liquid crystal display device to be obtained may not have sufficient strength with respect to the external pressure such as a pen input.
  • the cooling rate is less than 0.050° C./minute, about more than 27 hours are required for cooling, for example, from 100° C. to 20° C. Therefore, it takes a long time to produce a liquid crystal display device, which is not industrially effective. Furthermore, it is difficult to produce an apparatus which is capable of achieving such a slow rate of cooling.
  • the predetermined portions of the liquid crystal cell can be irradiated with light.
  • the conditions of the light irradiation after the cooling can be arbitrarily set by those skilled in the art.
  • the preferable conditions of light irradiation used in the step of selectively radiating light having different irradiation intensities can be used.
  • the amount of the light irradiation during the light irradiation after the cooling is desirably about 800 mJ/cm 2 to about 5000 mJ/cm 2 . When the amount of the light irradiation is less than 800 mJ/cm 2 , the polymer walls may not be sufficiently formed.
  • the liquid crystal may adversely effect on the alignment layer.
  • an unreacted material remaining in the polymer walls is cured, whereby the sufficiently cross-linked polymer walls 104 can be obtained.
  • the liquid crystal display device of the present invention can be produced.
  • a phase different plate is provided on one of the substrates of the liquid crystal display device, and polarizing plates are provided on both the phase different plate and the other substrate, whereby a liquid crystal display device in an STN mode can be produced.
  • a reflection type liquid crystal display device can be produced by providing a reflective plate on one of the substrates of the liquid crystal display device.
  • the liquid crystal regions 103 in which the liquid crystal is concentrated are formed in the pixel portions, and a polymer material used for forming the polymer walls does not remain at the interface between the liquid crystal regions 103 and the alignment layer.
  • the liquid crystal display device has a satisfactory alignment state.
  • the polymer walls 104 are formed without incorporating the liquid crystal, and in the pixel portions of the liquid crystal display device, the liquid crystal regions 103 having a shape and an area almost identical with those of the overlapping portions of the transparent electrodes 102a and 102b are formed without the polymer walls 104 being formed therein.
  • the reaction heat generated by polymerization was measured by a photochemical reaction differential thermal calorimeter (PDC) (PDC121; manufactured by Seiko Denshi Kogyo Kabushiki Kaisha).
  • PDC photochemical reaction differential thermal calorimeter
  • This reaction heat generated by the polymerization depends on the type of molecules to be reacted, and the reaction heat generated by a predetermined amount of molecules during a particular reaction is constant.
  • the polymerization rate of a photopolymerizable monomer in a liquid crystal solution can be calculated by measuring the changes with time in generated reaction heat and the amount of the photopolymerizable monomer reacted per unit time from the reaction heat.
  • FIG. 2 shows the changes with time in reaction heat generated during the polymerization reaction of a conventional photopolymerizable monomer.
  • the reaction heat generated by the polymerization is integrated on a time basis, whereby the stages of the polymerization reaction, i.e., the changes with time in the conversion of the photopolymerizable monomer contained in the irradiation intensity-dependent mixture are obtained (FIG. 3).
  • the maximum reaction rate corresponds to the slope of a tangent of an inflexion point B in FIG. 3, and the inflexion point B corresponds to a point at a time A where the amount of generated heat in FIG. 2 becomes maximum.
  • the values of the monomer conversion up to the inflexion point B calculated as the amount per unit time was used as a polymerization rate
  • a polymer chip remaining in pixels of the produced liquid crystal display device was observed with a microscope, and the remaining amount was evaluated as follows:
  • An ITO layer having a thickness of 200 nm was formed on substrates 101a and 101b made of 7059 glass (produced by Corning), respectively, by sputtering.
  • the ITO layer were patterned by photolithography, whereby a plurality of band-shaped transparent electrodes 102a and 102b with a width of 280 ⁇ m and an interval of 20 ⁇ m were formed on the substrates 101a and 101b, respectively.
  • an electrical insulating layer having a thickness of 100 nm made of SiO 2 was formed by sputtering on the transparent electrodes 102a and 102b, respectively.
  • an alignment layer having a thickness of 80 nm (S-150; produced by Nissan Chemical Industries, Ltd.) was formed on each of the electrical insulating layer. These alignment layer were subjected to rubbing with a nylon cloth.
  • the substrates 101a and 101b were attached to each other in such a manner that the rubbing direction was identical with a twist angle. Spacers were dispersed between the substrates 101a and 10b. The ends of the substrates 101a and 101b were attached to each other with a sealant so that an injection hole was formed in the periphery of the substrates 101a and 101b.
  • a mixed solution which includes 3 g of ZLI-4427 containing 0.3% by weight of chiral agent (S-811) (produced by Merck & Co., Inc.), 0.04 g of a polymerizable monomer represented by the following formula (II): ##STR5## 0.4 g of hexanediol dimethacrylate (HDDMA), and 0.008 g of Irgacure 651 (produced by CIBA-GEIGY Corporation) was injected between the attached substrates 101a and 101b by a known method. Since the opening ratio of the device was about 87%, the weight ratio of the liquid crystal to the total of the photopolymerizable monomer and the photopolymerization initiator was set to be 87:13.
  • S-811 produced by Merck & Co., Inc.
  • HDDMA hexanediol dimethacrylate
  • Irgacure 651 produced by CIBA-GEIGY Corporation
  • UV-light was radiated through both sides of the substrates 101a and 101b by a UV-lamp at 7 mW/cm 2 (365 nm.) for 4 minutes (irradiation amount: 1680 mJ/cm 2 ) at 100° C. so that the liquid crystal material between the substrates 101a and 101b assumed an isotropic state.
  • the pixel portions were formed in overlapping portions of the electrode portions respectively formed on a pair of substrates.
  • the non-pixel portions were formed in overlapping portions of the electrode portions on one substrate and the non-electrode portions on the other substrate and in overlapping portions of the non-electrode portions on both the substrates.
  • the intensities of UV-light radiated to the pixel portions and the non-pixel portions in the present example are shown in Table 2.
  • the polymerization rate of the photopolymerizable monomer contained in the irradiation intensity-dependent mixture in the pixel portions and the non-pixel portions, and the ratio of the polymerization rates are shown in Table 3.
  • the liquid crystal panel was slowly cooled from 100° C. to room temperature at a cooling rate of 0.12° C./minute (7° C./hour) in a cooling chamber.
  • the liquid crystal panel was irradiated with UV-light at 7 mW/cm 2 (365 nm.) for 2 minutes (irradiation amount: 840 mJ/cm 2 ) at room temperature through both sides of the substrates 101a and 10b.
  • the liquid crystal display device thus produced was observed with a microscope. This revealed that liquid crystal regions 103 in which the liquid crystal was concentrated were formed in pixel portions 107, and a satisfactory alignment state was obtained at the interface between the liquid crystal regions and the alignment layer without any remaining polymer. Furthermore, in the non-pixel portions, polymer walls 104 were formed without incorporating the liquid crystal. In the pixel portions, the liquid crystal regions 103 having a shape and an area almost identical with those of the overlapping portions of the transparent electrodes 102a and 102b were formed without any polymer wall 104.
  • a liquid crystal display device was produced in the same way as in Example 1, except that UV-light irradiation after the injection of the mixed solution and before the cooling was conducted at 5 mW/cm 2 (365 nm.) for 4 minutes (irradiation amount: 1200 mJ/cm 2 ).
  • the evaluation result of the liquid crystal display device thus obtained is shown in Table 4.
  • Liquid crystal display device were produced in the same way as in Example 1, except that UV-light irradiation after the injection of the mixed solution and before the cooling was conducted under the conditions shown in Table 4. The evaluation results of the liquid crystal display device thus obtained are shown in Table 4.
  • Liquid crystal display devices were produced in the same way as in Example 1, except for using mixed solutions containing a liquid crystal material, a photopolymerizable monomer, and a photopolymerization initiator which had contents shown in Table 5. The evaluation results of the liquid crystal display device thus obtained are shown in Table 5.
  • Liquid crystal display devices were produced in the same way as in Example 1, except for using mixed solutions containing a liquid crystal material, a photopolymerizable monomer, and a photopolymerization initiator which had contents shown in Table 5. The evaluation results of the liquid crystal display device thus obtained are shown in Table 5.
  • the ratio of polymerization rates varies depending upon the contents of the liquid crystal material, the photopolymerization initiator, and the photopolymerized monomer, and the liquid crystal display devices obtained at a ratio of polymerization rates of more than 1.1 are excellent.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 8% by weight of stearyl acrylate, 4% by weight of R-684 (produced by Nippon Kayaku Co., Ltd.), and 2% by weight of p-phenylstyrene were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus-obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 10% by weight of stearyl acrylate, 2% by weight of R-684 (produced by Nippon Kayaku Co., Ltd.), and 2% by weight of p-phenylstyrene were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 5% by weight of isobornyl acrylate and 5% by weight of HDDMA were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 8% by weight of acrylate and 2% by weight of HDDMA were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 3% by weight of R-694 (produced by Nippon Kayaku Co., Ltd.), 4% by weight of R-684 (produced by Nippon Kayaku Co., Ltd.), and 3% by weight of HDDMA were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 1% by weight of R-694 (produced by Nippon Kayaku Co., Ltd.), 4% by weight of R-684 (produced by Nippon Kayaku Co., Ltd.), and 5% by weight of HDDMA were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • liquid crystal display device was produced in the same way as in Example 1, except that 6% by weight of t-butyl methacrylate and 4% by weight of stearyl acrylate were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 2% by weight of t-butyl methacrylate and 8% by weight of stearyl acrylate were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 5% by weight of SR-2000 (produced by Nippon Kayaku Co., Ltd.) and 5% by weight of the compound represented by the above formula (II) were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 8% by weight of SR-2000 (produced by Nippon Kayaku Co., Ltd.) and 2% by weight of the compound represented by the above formula (II) were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 4% by weight of R-684 (produced by Nippon Kayaku Co., Ltd.) and 5% by weight of the compound represented by the above formula (II) were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 8% by weight of R-684 (produced by Nippon Kayaku Co., Ltd.) and 1% by weight of the compound represented by the above formula (II) were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 4% by weight of TMPTMA and 5% by weight of the compound represented by the above formula (II) were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 8% by weight of TMPTMA and 1% by weight of the compound represented by the above formula (II) were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 4% by weight of HDDMA, 3% by weight of the compound represented by the above formula (II), and 3% by weight of a compound represented by the following formula (III): ##STR6## were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • a liquid crystal display device was produced in the same way as in Example 1, except that 2% by weight of HDDMA, 4% by weight of the compound represented by the above formula (II), and 4% by weight of the compound represented by the above formula (III) were used as a photopolymerizable monomer.
  • the evaluation results of the liquid crystal display device thus obtained are shown in Table 6.
  • the ratio of polymerization rates varies depending upon the contents of the photopolymerizable monomer, and liquid crystal display devices obtained at a ratio of polymerization rates of 1.1 or more are excellent.
  • a liquid crystal display device was produced in the same way as in Example 1, except that UV-light irradiation after the injection of the mixed solution and before the cooling was conducted at 8 mW/cm 2 (365 nm.) for 200 seconds (irradiation amount: 1600 mJ/cm 2 ).
  • V-T voltage-transmittance
  • a liquid crystal display device was produced in the same way as in Example 1, except that UV-light irradiation after the injection of the mixed solution and before the cooling was conducted at 8 mW/cm 2 (365 nm.) for 400 seconds (irradiation amount: 3200 mJ/cm 2 ).
  • V-T voltage-transmittance
  • a liquid crystal display device was produced in the same way as in Example 1, except that UV-light irradiation after the injection of the mixed solution and before the cooling was conducted at 8 mW/cm 2 (365 nm.) for 100 seconds (irradiation amount: 800 mJ/cm 2 ).
  • V-T voltage-transmittance
  • the slope of the curves for the liquid crystal display devices produced in Examples 13 and 14 are steeper in a liquid crystal portion and have a higher threshold voltage, compared with the liquid crystal display device produced in Comparative Example 15. Therefore, in the liquid crystal display devices produced in Examples 13 and 14, the phase separation between the liquid crystal regions and the polymer walls are sufficiently achieved, and outstanding display performance is obtained.
  • a liquid crystal display device was produced in the same way as in Example 1, except that UV-light irradiation after the injection of the mixed solution and before the cooling was conducted at 8 mW/cm 2 (365 nm.) for 700 seconds (irradiation amount: 5600 mJ/cm 2 ).
  • the liquid crystal display device thus obtained was observed. This revealed that the resin of the polymer walls moved to the pixel portions and accumulated on the alignment layer; as a result, a uniform alignment state was not obtained due to the presence of a portion P 1 showing a normal alignment state and a porion P 2 of a low twisted domain as shown in FIG. 5.
  • a liquid crystal display device was produced in the same way as in Example 1, except that the cooling rate was set to be 1.0° C./minute.
  • the pressure resistance value (g/mm ⁇ ) of the liquid crystal display device was measured by using a push-pull gauge with a pen tip of 1 mm ⁇ .
  • the pressure resistance value thus obtained is shown in Table 8.
  • a liquid crystal display device was produced in the same way as in Example 1, except that the cooling rate was set to be 0.7° C./minute. Then, the pressure resistance value of the liquid crystal display device was measured in the same way as in Example 15. The pressure resistance value thus obtained is shown in Table 8.
  • a li quid crystal display device was produced in the same way as in Example 1, except that the cooling rate was set to be 0.3° C./minute. Then, the pressure resistance value of the liquid crystal display device was measured in the same way as in Example 15. The pressure resistance value thus obtained is shown in Table 8.
  • a liquid crystal display device was produced in the same way as in Example 1, except that the cooling rate was set to be 0.1° C./minute. Then, the pressure resistance value of the liquid crystal display device was measured in the same way as in Example 15. The pressure resistance value thus obtained is shown in Table 8.
  • a liquid crystal display device was produced in the same way as in Example 1, except that the cooling rate was set to be 0.05° C./minute. Then, the pressure resistance value of the liquid crystal display device was measured in the same way as in Example 15. The pressure resistance value thus obtained is shown in Table 8.
  • a liquid crystal display device was produced in the same way as in Example 1, except that the cooling rate was set to be 3.0° C./minute. Then, the pressure resistance value of the liquid crystal display device was measured in the same way as in Example p15. The pressure resistance value thus obtained is shown in Table 8.
  • a liquid crystal display device was produced in the same way as in Example 1, except that the cooling rate was set to be 1.2° C./minute. Then, the pressure resistance value of the liquid crystal display device was measured in the same way as in Example 15. The pressure resistance value thus obtained is shown in Table 8.
  • the pressure resistance value of the produced liquid crystal display device is likely to increase.
  • the amount of liquid crystal incorporated in the polymer walls is smaller in the liquid crystal display devices produced in Examples 15 through 19 than in those produced in Comparative Examples 17 and 18.
  • the liquid crystal display devices produced in Examples 15 through 19 have sufficient strength with respect to the external pressure such as a pen input.
  • the polymerization rate varies depending upon the type of the photopolymerizable monomer, a solvent to be used (liquid crystal in the present invention), the concentration thereof, temperature during light irradiation, and a blend ratio of a plurality of resins if used.
  • the polymerization rate hardly varies when irradiation intensity exceeds a certain value.
  • light with different irradiation intensities is selectively radiated. More specifically, light is radiated in the range of the irradiation intensities which cause the difference in polymerization rate of the photopolymerizable monomer contained in the irradiation intensity-dependent mixture with such reaction characteristics.
  • the polymer walls are formed in non-pixel portions and liquid crystal regions are formed in pixel portions.

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US10502999B2 (en) * 2014-08-29 2019-12-10 Lg Display Co., Ltd. Light controlling apparatus and method of fabricating the same
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